Azo dyestuffs and process of preparing them



Patented -May 20, 1930' UNITED STATES PATENT. OFFICE ERWIN HOFFA AND FRITZ Mfi'LLER, OF HOCHST-ON-THE-MAIN,' GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., 013 NEW YORK, N. Y.,- A CORPORATION OF DELAWARE AZO DY ESTUFFS AND PROCESS OF PREPARING THEM:

No Drawing. Application filed December 7, 1927, Serial No. 238,457, and in Germany December 13, 1926.

- This-invention relates to azo dyestuffs and processes of preparing them.

e have found that-by coupling with any coupling component a cyanogen aryldiazo compound prepared from an amine of the following formula:'

wherein one X stands for the group CN and the other Xs for hydrogen or any substituent, which latter may be of such a kind as to make the finally obtained dyestuff water-soluble or not, azo dyestuffs are obtained which when the components areselected in a suitable manner meet high requirements as regards fastness to kier-boiling and are distinguished by clear tints of excellent fastness to light.

The dyestuffs can be produced either in substance or on the fiber or 'on other substrata.

The following examples illustrate our invention, but they are not intended to limit it thereto:

1. Cotton fiber is padded in the usual manner with the following grounding l.'- quor: 8 pints by volume of formaldehyde of 30 per cent strength are added to asolution prepared from 8 parts by weight of 2.8-hydroxy-' naphthoic acid-4-chl0ro-2-anisidide, 16 parts by volume of sodium Turkey red oil, 16 parts tion is complete the whole is made up with cold water to 1000 parts by volume and neutralized with sodium acetate until the mass 2. The grounding liquor is prepared as follows: 3 parts by weight of diacetoacetic acidortho-tolidide, 6 parts by volume of sodium Turkey red oil of 50 per cent strength and 6 parts by volume of caustic soda solution of 34 B. are dissolved in 500 parts by volume of hot water, there are added thereto 28 parts by weight of crystallized sodium sulfate and the whole is made up with water to 1000 parts by volume. Cotton padded with this grounding liquor is developed with a diazo solution prepared as indicated in Example 1 to which there have further been added 1.5 parts by Volume of acetic acid of 50 per cent strength. A reddish-yellow tint is thus obtained having excellent properties as to fastness. The dyestuff has probably the following formula:

do-rrfi-QQnn-do cm I Hi by volume of caustic soda solution of 34 B. and 500 parts by volume of hot water, and the whole is made up with water to 1000 parts by volume. The diazo solution is prepared as follows: 2.6 parts by weight of 5-cyanogen- 2-toluidine are mixed, while stirring, with 5.2 parts by volume. of ll \'(.ll'0('lll0l'l0 acid of 22 B. and ice-cold uater, and to this mixture are added 1.4-1 parts by weight of sodium niirite dissolved in water. After the diazotizaa By substituting in Example 1 for the s parts by weight of 2.3-hydroxynaphthoic of 2.S-hydroxynaphthoic acid-a-naphthyl' amide and for the 2.6 parts by weight of 5 cyanogenQ-toluidine 2.5 parts by weight of 1- 7 NO H 4. 16.2 parts by weight of 4c-cyanogen-2 amino-l-benzoic acid are dissolved in 11 parts by weight of sodium carbonate and 250 parts of water, to this solution are added 7 parts by weight of sodium nitrite and then the mass is introduced at 0 0., while stirring, into a mixture of 40 parts by weight of-hydrochloric acid of 36 per cent strength and 200 parts of ice and water. The diazo solution is somewhat neutralized' by means of a dilute solution of sodium carbonate and clarified by filtering it. It is then run into a solution of 24.6 parts by Weight of sodium l-hydroxynaphthalene l-sulfonate in parts by 25 weight of sodium acetate and 350 parts of water. The dyestufi' separates in the form of orange-colored laminae. It dyes from an acid bath wool an orange tint of good fastness properties which by an after-treatment with a chromate is transformed into a reddishviolet of likewise good properties as to fastness.

' The following table indicates a number of dyestuffs which can be made in accordance with our present invention.

by diazotizing an arylamine of the following formula:

wherein one X stands for the group CN and the other Xs for hydrogen or any substitucnt, and coupling it with an azo component capable of being coupled with diazocolnpounds.

2. The process of preparing azo dyestuffs by diazotizing an arylamine of the following formula: NH,

wherein one X stands for the group -CN and the other Xs for hydrogen or any substituent which does not render the product soluble in Water, and coupling it with an azo component capable of being coupled with diazo compounds.

3. The process of preparing azo dyestufl's by diazotizing an arylamine of the'following formula:

Properties of the dyeing pro- Diazo-compound of Coupled with duccd on the fibre l-amino-3-cyanogen-2-methylbenzene I-amlno-2-cyanogen-4-ehlorobenzene 1-amino-2-eyanogen-4-chlorobenzene 1-amlno-2-cyanogen-4-chlorobenzene 1-amlno-2-eyanogen-4-ehlorobenzene l-amino-2.1-dimethyl-5-cyanogcn-benl-a lii iiio-3-cyanogen-6-chlorobenzene l-amino-3-cyanogen-6-chlorohenzene I-amino-3-eyanogen-6-chlorobenzene 1-amino-3-cyanogen-6-chlorobenzene 1-amlno-2-eyanogen-5-methy1henzene I-amlno-Z-cyanogen-E-methylbenzene 1-amino-2-cyanogen-5-methylbenzene l-amino-2-cyanogen-5-chlorbenzene 2.31-hydr1oic1ynaphthoic acid-2'-methyl-4-chloro- -fllll l. e

2.3-hyd roxynaphthoic acid-1'-naphthylamide 2.3-hydroxynaphthoie acid-anilide 2.3-hydroxynaphthoic aeid-2'-t01uidide 2.3illydrp 11ynaphth0ic acid-2'-methyl-4'-ch1oro- -am it e 2.3-hydroxynaphthoie acid-2'-methyl-1'-anilide 2.31-hydrpxyl1aphthoic acid-2'-methyl-4'-chloro1 2.?l-laydroxynaphthoic aeid-4'-methoxy 1 ani- 2.3-hydroxynaphthoic acld-2'-methyl-1-anilide 2.3-hydroxynaphthoic aeid-1'-anilide 2.31-hydrloxynaphthoic aeid-2-methyl-4'-ehloro- '-ani e 2.3-hydroxynaphthoic acid-1-anilide 2.3-hydroxynaphthoic acld-2'-methoxy-5'-chloro-1anilide I 2.3-hydroxynaphthoic acid-2 methyl4 chloro- 1 -amlide Bright scarlet fast to light Bright claret-rod fast to light Bl'igliltt reddishbrange fast to Brigg yellowish scarlet fast to yellowish scarlet fast to Bright scarlet of good fastness yellowish scarlet fast to Brlightt yellowish scarlet fast to Bright yellowish scarlet fast to li"ht Brightyellowish scarlet fast to "llt Brligigt reddish-orange fast to Bright scarlet of good tastness to light Orange of good fastness to light Bright' reddish-orange ofgoodfastness to light Insteadof the 2.3-hydroxynaphthoic acid 'arylides there may be used with a similar result as coupling components ,B-ketocarboxylic acid-arylides.

We claim: 1. The process of preparing azo dyestuffs wherein one X stands for the group CN and the other Xs for hydrogen or any substituent which does not render the product soluble in water, and coupling it with a 2.3- hydroxynaphthoic acid-arylamide.

4. The process of preparing azo dyestufls pounds, said products by diazotizing an arylamine of the following formula:

. X ON wherein X stands for hydrogen or any sub-.

stituent which does not render the product soluble in water and coupling it with a 2.3-hydroxynaphthoie acid-arylamide.

5. The process of preparing azo dyestufls by diazotizing an arylamine of the following formula:

I NH;

1 x ii I H CN 1 n i v wherein X stands for hydrogen or any substituent which does not render the product soluble in water and coupling it with a -2.3-hydroxynaphthoic acid-arylamide.

6. The process of preparing azo dyestuffs by diazotizing 1-amino-3-c anogen-G-methylbenzene of the following ormula:

and coupling it with a 2.3 hydroxynaphthoic acid-arylamide.

7. As new products, azo dyestufis substantially identical with dyestuffs obtainable by diazotiz'ing an arylamine of the following formula 'wherein one X stands for the group -CN and the other Xs for hydrogen or any substituent which does not render the product soluble in water, and coupling it with an azo componentcapable of being coupled with diazocompounds, said products being powders the color of which varies from yellow to blue and yellow to brown;

9. As newv products, azo

dyestuffs of the following formula: 4 I

wherein one X stands for the group CN, the other Xs for hydrogen or any substituent which does not render the product soluble in water and the aryl stands for an aryl group the hydrogen atoms of which may be substituted or not, said products being powders the color of which varies from yellow to blue and from yellow to brown.

10. As new products, azo dyestuffs of the following formula:

OE CO.NH.aryl

wherein X stands for hydrogen or any substituent which does not render the product soluble in water and the aryl stands for an aryl group the hydrogen atoms of which may be substituted or not, said products being yellowish-red to bluish-red and yellowish-red to brownish-red powders and yielding when produced on the fiber dyeings of very good fastness properties.

11. As new products, azo following formula:

dyestufls of the OH CO.NB.aryl

wherein X stands for hydrogen or any substituent which does not render the product soluble in water and the aryl stands for an aryl group the hydrogen atoms of which may be substituted or not, said products being yellowish-red to bluish-red and yellowish-red to brownish-red powders and yielding when produced on the fiber dyeings of very good fastness properties.

- 12. As new products, azo dyestufi's of the following formula:

on CO.NH.aryl

5 v N=N wherein aryl stands for an 'aryl group the hydrogen atoms of which may be substituted or not, said products being yellowish-red to bluish-red and yellowish-red'to brownish-red powders andyielding when produced on the fiber dyeings of Very good fastness properties. 13, As a new product, the dyestufi of the following constitution on O0-NH 4 NFN said product being a bluish-red owder and yielding when produced on the fi er dyeings of excellent fastness to light. 1 1

In testimony whereof, we aflix our signatures. ERWIN H OFFA. FRITZ MULLER. 

